ES2399904T3 - 3-methyl oxetanmethanol derivatives and their use in perfume compositions - Google Patents

Abstract

A method of enhancing, enhancing or modifying a fragrance formulation by adding an acceptable olfactory amount of a compound of formula (I): wherein R is selected from the group consisting of C (CH3) C3H7, C (CH3) C4H9, C (CH3) C4H8, C (CH3) C2H4CHC2H4, C (CH3) phenyl, C (CH3) CN, C (CH3) COCH3, C (CH3) COC3H7, C (CH3) COC3H6, C (CH3) COCH2CHC2H4.

Description

3-methyl oxetanmethanol derivatives and their use in perfume compositions

5 Field of the invention

The present invention relates to new derivatives of 3-methyl oxetanmethanol and its use as fragrance chemicals suitable for incorporation into fine fragrances, cosmetics, toiletries and related applications.

Background of the invention

There is a continuing need in the fragrance industry to provide new chemicals to give perfumers and others the ability to create new fragrances for perfumes, colognes and personal care products. Those skilled in the art appreciate how differences in the chemical structure of the molecule

15 can produce significant differences in the smell, notes and characteristics of the molecule. These variations and the continuing need to discover and use new chemicals in the development of new fragrances allow perfumers to apply the new compounds in the creation of new fragrances. The preparation of the 3-methyl oxetanmethanol compound is disclosed by Pattison (J. Amer. Chem. Soc., 79, p3455, 1957).

Compendium of the invention

The present invention provides new chemicals, and the use of chemicals to increase the fragrance of perfumes, eau de colognes, colognes, personal products and the like. More specifically, the present invention is directed to a method of improving, increasing or modifying a fragrance formulation by

Addition of an acceptable olfactory amount of a compound represented by the general structure of the formula I shown below:

Formula I

wherein R is as defined in the claims. Also disclosed is a fragrance formulation containing an effective olfactory amount of the compound of the formula I, and a fragrance product containing a compound of the formula I.

In another embodiment, the present invention is directed to a method for increasing a perfume by incorporating an acceptable olfactory amount of compounds represented by the general structure of formula II shown below:

Formula II

wherein R is selected from the group consisting of linear, branched, cyclic or aromatic hydrocarbon groups containing single and / or double bonds; carbonyls and carboxy compounds.

In another embodiment of the invention, new compounds represented by the following structures are provided:

Formula IV Formula V

5 These and other embodiments of the present invention will be apparent upon reading the following specification.

Detailed description of the invention

In formula II above R is selected from the group consisting of linear, branched, cyclic or aromatic hydrocarbon groups containing single and / or double bonds; carbonyls and carboxy compounds.

Suitable linear hydrocarbon groups include ethyl, propyl, butyl, cyclopentyl, cyclohexyl and the like. Suitable branched hydrocarbon groups include isopropyl, sec-butyl, tert-butyl, 2-ethyl-propyl, and the like. Suitable hydrocarbon groups containing double and triple bonds include ethene, propene, 1-butene,

15 2-Butene, penta-1,3-diene, hepta-1,3,5-triene, butyne, hex-1-ino, and the like. Suitable cyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. Suitable aromatic groups include benzyl, phenylethyl and the like. Suitable carbonyls include derivatives of aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, and the like; ketone derivatives such as acetone, methyl ethyl ketone, methyl n-propyl ketone, diethyl ketone, 2-hexanone, 3-hexanone and the like.

In the preferred embodiment of the invention, the compounds of formula I used in the present invention are represented by the following structures:

    Formula III Formula IV

Formula V

Those skilled in the art will appreciate that the compound of formula III is 3-methyl-3 - [(2-propenyloxy) methyl] oxetane, the compound of formula IV is 3-methyl-3 - [(3-methylbutyl) oxy] methyl oxetane, the compound of formula V is 3,7-dimethyl-1 - [(3-methylxetan-3-yl) methyloxy] octa-2,6-diene.

The table below lists additional compounds derived from the formula I described in the present invention: With reference to the compounds of our invention, the synthesis is effected by the reaction of 3-methyl oxetamethanol with methyl ether with catalysis of sodium methoxide to deliver the desired compound according to the scheme below:

R

Compound

C (CH3) C3H7

 3-methyl-3- (3-methyl-hex-2-ethylxymethyl) oxetane

C (CH3) C4H9

 3-methyl-3- (3-methyl-hept-2-ethylxymethyl) oxetane

C (CH3) C4H8

 3-methyl-3- (3-methyl-hepta-2,6-dienyloxymethyl) oxetane

C (CH3) C2H4CHC2H4

 3- (5-Cyclopropyl-3-methyl-pent-2-enyloxymethyl) -3-methyl-oxetane

C (CH3) phenyl

 3- (3-Cyclohexyl-but-2-enyloxymethyl) -3-methyl-oxetane

C (CH3) CN

 2-methyl-4- (3-methyl-oxetan-3-ylmethoxy) -but-2-enonitrile

C (CH3) COCH3

 3-methyl-5- (3-methyl-oxetan-3-ylmethoxy) -pent-3-en-2-one

C (CH3) COC3H7

 3-methyl-1- (3-methyl-oxetan-3-ylmethoxy) -hept-2-en-4-one

C (CH3) COC3H6

 5-methyl-7- (3-methyl-oxetan-3-ylmethoxy) -hepta-1,5-dien-4-one

C (CH3) COCH2CHC2H4

 1-Cyclopropyl-3-methyl-5- (3-methyl-oxetan-3-ylmethoxy) -pent-3-en-2-one

base is added to a mixture of 3-methyl oxetanmethanol and an ester which is then heated to a temperature ranging from 60 ° C to 150 ° C, most preferably from 90 ° C to 120 ° C. Methanol is distilled in the head and removed from the reaction. The mixture is cooled to 25 ° C and neutralized with acetic acid. The reaction mass is washed with 10% aqueous sodium chloride solution and the crude product is purified by distillation. The reaction is

10 produces in a yield of 70-90% molar based on ester, methyl benzoate. The preparation of the 3-methyl oxetanmethanol compound is disclosed by Pattison (J. Amer. Chem. Soc., 79, p3455, 1957).

In another embodiment, the present invention is directed to a method for increasing a perfume by incorporating an acceptable olfactory amount of compounds represented by the general structure of formula II shown below:

Formula II

Wherein R is selected from the group consisting of linear, branched, cyclic or aromatic hydrocarbon groups containing single and / or double bonds; carbonyls and carboxy compounds.

Suitable linear hydrocarbon groups include ethyl, propyl, butyl, cyclopentyl, cyclohexyl and the like. Suitable branched hydrocarbon groups include isopropyl, sec-butyl, tert-butyl, 2-ethyl-propyl, and the like. Suitable hydrocarbon groups containing double and triple bonds include ethene, propene, 1-butene, 2-butene, penta-1,3-diene, hepta-1,3,5-triene, butyne, hex-1-ino, and the like Suitable cyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. Suitable aromatic groups include phenyl, benzyl, phenylethyl and the like. Suitable carbonyls include derivatives of aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, and the like; ketone derivatives such

30 such as acetone, methyl ethyl ketone, methyl n-propyl ketone, diethyl ketone, 2-hexanone, 3-hexanone and the like.

The table below lists some of the compounds derived from the formula II described in the present invention:

R

Compound

C2H5

 3-ethoxymethyl-3-methyl-oxetane

C2H4

 3-methyl-3-vinylxymethyl-oxetane

CH2CH (CH3) 2

 3-isobutoxymethyl-3-methyl-oxetane

Car3

2 (3-Methylxetan-3-yl) methyl methyl acetate

COCH2CH2CH3

(3-Methylxetan-3-yl) methyl methylpropanoate

COCH2CH2CH2CH3

(3-Methylxetan-3-yl) methyl methylbutanoate

COCH2CH2CH2CH2CH3

(3-Methylxetan-3-yl) methyl methylpentanoate

COOCH3

2- (3-Methylxetan-3-yloxy) ethyl acetate

COOCH2CH2CH3

Ethyl 2- (3-methylxetan-3-yloxy) propanoate

COO (CH2) 6CH3

Ethyl 2- (3-methylxetan-3-yloxy) heptanoate

The synthesis of these compounds is described in the examples below.

The use of this compound is widely applicable in current perfumery products, including the preparation of perfumes and colognes, the scented of personal care products such as soaps, shower gels and

40 hair care products as well as air fresheners, candles and cosmetic products. The compound can also be used to perfume candles and cleaning agents, such as, but not limited to, soaps, detergents, dishwashing materials, scrubbing compositions, glass cleaners and the like.

In these preparations, the compound of the present invention can be used alone or in combination with other fragrance compositions, solvents, adjuvants and the like. Those skilled in the art will appreciate the nature and variety of the other ingredients that can be used in combination with the compound of the present invention.

5 Many types of fragrances can be used in the present invention, the only limitation is compatibility with the other components used. Suitable fragrances include, but are not limited to fruits such as almond, apple, cherry, grape, pear, pineapple, orange, strawberry, raspberry; musk, flower aromas, such as lavender, pink, iris and carnation. Other pleasant aromas include herbal and forest aromas derived from pine, spruce and other scents from the forest. Fragrances can also be derived from various oils,

10 such as essential oils, or of plant materials such as peppermint, mint and the like.

A list of suitable fragrances is provided in US Patent No. 4,534,891, the content of which is incorporated by reference as if fully explained.

15 Another source of suitable fragrances is in Perfumes, Cosmetics and Soaps, Second Edition, edited by WA Poucher, 1959. Among the fragrances provided in this treaty are acacia, cassia, chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle , hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly cut hay, orange blossoms, orchid, reseda, sweet pea, clover, tuberose, vanilla, violet, wallflower, and the like.

As used herein, it is understood that effective olfactory amount means the amount of compound in perfume compositions to which the individual component will contribute with its particular olfactory characteristics, but the olfactory effect of the perfume composition will be the sum of the effects of each of the ingredients of the perfume or fragrance. Therefore, the compounds of the invention can be used to alter the aroma characteristics of the perfume composition by modifying the olfactory reaction contributed by another

25 ingredient in the composition. The amount will vary depending on many factors including other ingredients, their relative amounts and the desired effect.

The level of the compound of the invention employed in the scented article ranges from about 0.005 to about 10 percent by weight, preferably from about 0.1 to

30 about 8 and most preferably from about 0.5 to about 5 percent by weight. In addition to the compounds, other agents can be used together with the fragrance. Well-known materials such as surfactants, emulsifiers and polymers can also be used to encapsulate the fragrance without departing from the scope of the present invention.

Another method of describing the level of the compound of the invention in the scented composition, that is, the compounds as a percentage by weight of the materials added to give the desired fragrance. The compounds of the invention can vary widely from 0.005 to about 10 percent by weight of the scented composition, and preferably from about 0.1 to about 5 percent by weight. Those skilled in the art will be able to employ the desired level of the compound of the invention to

40 provide the desired fragrance and intensity.

The following are provided as specific embodiments of the present invention. Other modifications of this invention will be readily apparent to those skilled in the art, without departing from the scope of this invention. As used herein, all percentages are percentages by weight.

45 IFF is intended to be understood as International Flavors & Fragances Inc.

Example 1. Preparation of esters of the present invention

The following reaction sequence was used to prepare the specific compounds described by the NMR 50 data as shown below:

The 3-methyl oxetanmethanol (1.3 mol) and ester (1 mol) are combined to which sodium methoxide (0.2 mol) is added. The resulting mixture is heated from 90 ° C to 120 ° C, and methanol is removed from the reaction through a trap.

55 Dean-Stark. The reaction is aged until no more methanol is produced and the GC analysis of the reaction indicates that less than 10% of the starting ester is present. The reaction mass is cooled to room temperature and neutralized with acetic acid (0.5 mol). The reaction is washed with 10% aqueous sodium chloride solution. The crude reaction mass is purified by fractional distillation to give the product ester.

The esters are synthesized according to the previous general scheme with the following specific examples. The equivalents shown are molar equivalents based on the initial esters, the yields are distilled chemical yields based on the initial esters.

(3-Methylxetan-3-yl)) methyl 2-methylpropanoate

1.3 equivalent 3-methylxetan methanol, 1 equivalent methyl 2-methylpropanoate, 0.2 equivalent sodium methoxide, quench, 0.5 equivalent acetic acid, with 10% sodium chloride solution, yield = 88%. Smell: fruit.

1.20 ppm (d, 6H, J = 7.01 Hz) 1.34 ppm (s, 3H) 2.61 ppm (septet, 1H, J = 6.99 Hz) 4.16 ppm (s, 2H, d) 4.38 ppm (d, 2H, J = 5.93 Hz) 4.53 ppm (d, 2H, J = 5.93 Hz)

(3-Methylxetan-3-yl)) methyl 2-methylpentanoate

1.3 equivalent 3-methylxetan methanol, 1 equivalent methyl 2-methylpentanoate, 0.2 equivalent sodium methoxide, quench, 0.5 equivalent acetic acid, with 10% sodium chloride solution, yield = 80%. Smell: apple-like fruit.

0.91 ppm (t, 3H, J = 7.21 Hz) 1.17 ppm (d, 3H, J = 7.00 Hz) 1.32 ppm (m, 1H) 1.34 ppm (s, 3H) 1.36 ppm (m, 2H) 1.66 ppm (m, 1H) 2.51 ppm (sextet, 1H, J = 6.95 Hz) 4.16 ppm (s, 2H) 4.38 ppm (d, 2H, J = 5.94 Hz) 4.53 ppm (d, 2H, J = 5.92 Hz)

(3-Methylxetan-3-yl)) methyl 3-methylbutanoate

1.3 equivalent 3-methylxetan methanol, 1 equivalent methyl 3-methylbutanoate, 0.2 equivalent sodium methoxide, quench, 0.5 equivalent acetic acid, with 10% sodium chloride solution, yield = 90%. Smell: tropical fruit type

0.97 ppm (d, 6H, J = 6.62 Hz) 1.34 ppm (s, 3H) 2.12 ppm (m, 1H) 2.25 ppm (d, 2H, J = 7.30 Hz) 4.17 ppm (s, 2H) 4.38 ppm (d, 2H, J = 5.95 Hz) 4.52 ppm (d, 2H, J = 5.95 Hz)

(3-Methylxetan-3-yl)) methyl (6E) -3,7-dimethyloct-6-enoate

1,3 equivalents 3-methylxetan methanol, (6E) -3,7-dimethyloct-6-enoate methyl 1 equivalent, 0.2 equivalent sodium methoxide, quench, 0.5 equivalent acetic acid, with sodium chloride solution at 10%, yield = 86%. Smell: weak fruit

0.96 ppm (d, 3H, J = 6.64 Hz) 1.09-1.31 ppm (m, 1H) 1.34 ppm (s, 4H) 1.60 ppm (s, 3H) 1.68 ppm (s, 3H) 1.93-2.07 ppm (m, 3H) 2.18 ppm (d, 1H, J = 14.69 Hz, of d, J = 8.13 Hz) 2.37 ppm ( d, 1H, J = 14.69 Hz, of d, J = 6.00 Hz) 4.17 ppm (s, 2H) 4.38 ppm (d, 2H, J = 5.94 Hz) 4.52 ppm (d, 2H, J = 5.94 Hz) 5.08 ppm (t, 1H, J = 7.10 Hz)

(3-Methylxetan-3-yl)) methyl octanoate

1.3 equivalent 3-methylxetan methanol, 1 equivalent methyl octanoate, 0.2 equivalent sodium methoxide, quench, 0.5 equivalent acetic acid, with 10% sodium chloride solution, yield = 90%. Smell: similar to weak forest

0.88 ppm (t, 3H, J = 6.85 Hz) 1.27-1.32 ppm (m, 8H) 1.34 ppm (s, 3H) 1.64 ppm (pentet, 2H, J = 7 , 38 Hz) 2.36 ppm (t, 2H, J = 7.54 Hz) 4.16 ppm (s, 2H) 4.39 ppm (d, 2H, J = 5.94 Hz) 4.52 ppm ( d, 2H, J = 5.93 Hz)

The following 3-methyl oxetanmethanol esters were prepared as cited in the references provided.

Kanoh, S; Naka, M; Nishimura, T; Motoi, M, Tetrahedron 58, 7049-64, 2002. Rakus, K; Verevkin, S; Peng, W; Beckhous, H; Ruchardt, C, Liebigs Ann. Org. Bioorg Chem. 12, 2059-68, 1995. Give it, J; Fredriksen, S, Acta Chemica Scandinavica 45, 82-91, 1991. Corey, E; Natarajan, R, Tetrahedron Lett. P5571-5574, 1983.

(3-Methylxetan-3-yl) methyl hexanoate

Smell: sour acid

0.90 ppm (t, 3H, J = 6.95 Hz) 1.31-1.33 ppm (m, 4H) 1.34 ppm (s, 3H) 1.65 ppm (pentet, 2H, J = 7 , 44 Hz) 2.36 ppm (t, 2H, J = 7.54 Hz) 4.16 ppm (s, 2H) 4.38 ppm (d, 2H, J = 5.92 Hz) 4.52 ppm ( d, 2H, J = 5.91 Hz)

(3-Methylxetan-3-yl) methyl benzoate Smell: not described 5

1.42 ppm (s, 3H) 4.39 ppm (s, 2H) 4.45 ppm (d, 2H, J = 5.93 Hz) 4.64 ppm (d, 2H, J = 5.93 Hz) 7.46 ppm (t, 2H, J = 7.82 Hz) 7.56 ppm (t, 1H, J = 7.42 Hz) 8.07 ppm (d, 2H, J = 7.77 Hz) Acetate (3-Methylxetan-3-yl) methyl Odor: strawberry-like fruit 1.34 ppm (s, 3H) 2.10 ppm (s, 3H) 4.16 ppm (s, 2H,) 4.37 ppm (d , 2H, J = 5.94 Hz) 4.51 ppm (d, 2H, J = 5.94 Hz)

15 (3-Methylxetan-3-yl) methyl propanoate Odor: fruity type 1.17 ppm (t, 3H, J = 7.57 Hz) 1.34 ppm (s, 3H) 2.39 ppm (q, 1H, J = 7.58 Hz) 4.17 ppm (s, 2H) 4.38 ppm (d, 2H, J =

5.94 Hz) 4.52 ppm (d, 2H, J = 5.94 Hz) (3-Methylxetan-3-yl) methyl heptanoate Smell: pineapple-like fruit

25 0.89 ppm (t, 3H, J = 6.79 Hz) 1.30 ppm (s, 3H) 1.34 ppm (s, 6H) 1.64 ppm (m, 2H) 2.36 ppm (t , 2H, J = 7.52 Hz) 4.16 ppm (s, 2H) 4.38 ppm (d, 2H, J = 5.94 Hz) 4.52 ppm (d, 2H, J = 5.94 Hz )

(3-Methylxetan-3-yl) methyl butyrate Odor: fruity type 0.97 ppm (t, 3H, J = 7.42 Hz) 1.34 ppm (s, 3H) 1.68 ppm (sextet, 2H , J = 7.32 Hz) 2.34 ppm (t, 2H, J = 7.41 Hz)

4.17 ppm (s, 2H) 4.38 ppm (d, 2H, J = 5.95 Hz) 4.52 ppm (d, 2H, J = 5.96 Hz) 35 3-Methylxetan-3-yl ester 3-methyl-but-2-enoic acid methyl

Odor: green metallic type 1.35 ppm (s, 3H) 1.92 ppm (d, 3H, J = 1.32 Hz) 2.18 ppm (d, 3H, J = 1.26 Hz) 4.17 ppm (s, 2H) 4.38 ppm (d, 2H, J = 5.92 Hz) 4.54 ppm (d, 2H, J = 5.93 Hz) 5.73 ppm (t, 1H, J = 1 , 32 Hz)

Example 2. Preparation of ethers of the present invention

The following reaction sequence was used to prepare the specific compounds described by the NMR data shown below:

The 3-methyl oxetanmethanol (1 mol) is dissolved in THF (500 ml) and fed into a 60% sodium hydride dispersion (1.1 mol) in THF (500 ml) at 0 ° C. After the evolution of hydrogen gas, the chloride (1.1 mol) is added to the reaction at room temperature. The reaction is aged for 2-4 hours. The reaction is extinguished when GC analysis indicates that less than 10% of the initial alcohol is present. The reaction mass is washed with a 10% aqueous sodium chloride solution. The crude reaction mass is purified by distillation.

55 fractional giving the product.

The ethers are synthesized according to the previous general scheme with the following specific examples. The equivalents shown are molar equivalents based on the initial alcohol, the yields are distilled chemical yields based on the initial alcohol.

Preparation of formula III

The 3-methyl oxetanmethanol (1 mol) is dissolved in THF (500 ml) and fed into a 60% sodium hydride dispersion (1.1 mol) in THF (500 ml) at 0 ° C. After the evolution of hydrogen gas, allyl chloride (1.1 mol) is added to the reaction at room temperature. The reaction is aged for 2-4 hours. The reaction is extinguished when GC analysis indicates that less than 10% of the initial alcohol is present. The reaction mass is washed with a 10% aqueous sodium chloride solution. The crude reaction mass is purified by fractional distillation to give 114 g of 3-allyloxymethyl-3-methyl-oxetane.

Smell: waxy similar to mushroom

1.32 ppm (s, 3H) 3.50 ppm (s, 2H) 4.03 ppm (d, 2H, J = 5.58 Hz, of t, J = 1.43 Hz) 4.36 ppm (d , 2H, J = 5.74 Hz) 4.51 ppm (d, 2H, J = 5.74 Hz) 5.19 ppm (d, 1H, J = 10.41 Hz, of d, J = 1.70 Hz) 5.28 ppm (d, 1H, J = 17.25 Hz, of d, J = 1.70 Hz) 5.91 ppm (d, 1H, J = 17.24 Hz, of d, J = 10 , 40 Hz, of t, J = 5,553 Hz)

Preparation of formula IV

The 3-methyl oxetanmethanol (1 mol) is dissolved in THF (500 ml) and fed into a 60% sodium hydride dispersion (1.1 mol) in THF (500 ml) at 0 ° C. After the evolution of hydrogen gas, the prenyl chloride (1.1 mol) is added to the reaction at room temperature. The reaction is aged for 2-4 hours. The reaction is extinguished when GC analysis indicates that less than 10% of the initial alcohol is present. The reaction mass is washed with a 10% aqueous sodium chloride solution. The crude reaction mass is purified by fractional distillation giving 136 g of 3-methyl-3 - {[3-methylbut-2-en-1-yloxy] methyl} oxetane.

Smell: floral type thrush

1.32 ppm (s, 3H) 1.68 ppm (s, 3H) 1.76 ppm (s, 3H) 3.49 ppm (s, 2H) 4.01 ppm (d, 2H, J = 6.83 Hz) 4.36 ppm (d, 2H, J = 5.74 Hz) 4.49 ppm (d, 2H, J = 5.96 Hz) 5.35 ppm (t, 1H, J = 6.83 Hz)

Preparation of formula V

The 3-methyl oxetanmethanol (1 mol) is dissolved in THF (500 ml) and fed into a 60% sodium hydride dispersion (1.1 mol) in THF (500 ml) at 0 ° C. After the evolution of hydrogen gas, the prenyl chloride (1.1 mol) is added to the reaction at room temperature. The reaction is aged for 2-4 hours. The reaction is extinguished when GC analysis indicates that less than 10% of the initial alcohol is present. The reaction mass is washed with a 10% aqueous sodium chloride solution. The crude reaction mass is purified by fractional distillation to give 190 g of (2E, 6E) -3,7-dimethyl-1 - [(3-methylxetan-3-yl) methyloxy] octa-2,6-diene

Smell: lemon-like sweet

1.32 ppm (s, 3H) 1.61 ppm (s, 3H) 1.68 ppm (2s, 6H) 2.05-2.10 ppm (m, 4H) 3.49 ppm (s, 2H) 4 , 04 ppm (d, 2H, J = 6.70 Hz) 4.36 ppm (d, 2H, J = 5.73 Hz) 4.50 ppm (d, 2H, J = 5.71 Hz) 5.09 ppm (t, 1H, J = 6.81 Hz, of t, J = 1.33 Hz) 5.34 ppm (t, 1H, J = 6.67 Hz, of d, J = 1.19 Hz)

3 - {[(2E) -but-2-en-1-yloxy] methyl} -3-methylxetane

Odor: rough green similar to octencarbonate.

1.32 ppm (s, 3H) 1.8 ppm (s, 2H) 3.48 ppm (s, 2H) 3.96 ppm (d, 2H, J = 6.13 Hz) 4.36 ppm (d, 2H, J = 5.74 Hz) 4.50 ppm (d, 2H, J = 5.73 Hz) 5.54-5.77 ppm (m, 2H)

The following ethers of 3-methyl oxetanmethanol were prepared as cited in the references provided.

Blaskovich, M; Lajoie, G, J. Amer. Chem. Soc. 115, p5021-30, 1993. Gorin et al., J. Appl. Chem.USSR, 42, p1095, 1969.

3-methoxymethyl-3-methyl-oxetane

Odor: solvent similar to glue

1.31 ppm (s, 3H) 3.40 ppm (s, 3H) 3.45 ppm (s, 2H) 4.35 ppm (d, 2H, J = 5.74 Hz) 4.50 ppm (d, 2H, J = 5.75 Hz)

3-methyl-3 - {[(2-methylprop-2-en-1-yl) oxy] methyl} oxetane

Smell: strong, green solvent type.

1.35 ppm (s, 3H) 1.92 ppm (d, 3H, J = 1.32 Hz) 2.18 ppm (d, 3H, J = 1.26 Hz) 4.17 ppm (s, 2H) 4.38 ppm (d, 2H, J = 5.92 Hz) 4.54 ppm (d, 2H, J = 5.93 Hz) 5.73 ppm (t, 1H, J = 1.32 Hz)

Example 3. Preparation of carbonate materials of the present invention

The following reaction sequence was used to prepare the specific compounds described by the NMR data shown below:

3-Methylxetane methanol (1 mol) and dimethylcarbonate (1.5 mol) are combined to which sodium methoxide (0.2 mol) is added. The resulting mixture is heated from 90 ° C to 120 ° C, and the methanol is removed from the reaction through a Dean-Stark trap. The reaction is aged until no more methanol is produced and the GC analysis of the

15 reaction indicates that less than 10% of the initial alcohol is present. The reaction mass is cooled to room temperature and neutralized with acetic acid (0.5 mol). The reaction is washed with a 10% sodium chloride solution.

The crude reaction mass is purified by fractional distillation to give the product carbonate.

20 Carbonates are synthesized according to the previous general scheme with the following specific examples. The equivalents shown are molar equivalents based on the initial alcohol, the yields are distilled chemical yields based on the initial alcohol.

2- 2- (3-Methylxetan-3-yloxy) ethyl acetate

3-methylxetane methanol 1 equivalent, 1.5 equivalent diethylcarbonate, 0.2 equivalent sodium ethoxide, quench, 0.5 equivalent acetic acid, with 10% sodium chloride solution, yield = 85%.

30 Smell: weak floral

1.30 ppm (t, 3H, J = 7.18 Hz) 1.34 ppm (s, 3H) 4.14 ppm (q, 2H, J = 7.14 Hz) 4.17 ppm (s, 2H) 4.25 ppm (d, 2H, J = 5.65 Hz) 4.38 ppm (d, 2H, J = 5.65 Hz)

Incorporation of 3-methyl-3 - {[3-methylbut-2-en-1-yloxy] methyl} oxetane in a fragrance formulation

A fragrance was prepared according to the following formulation:

Material

 Parts

TRIPLAL® (IFF)

0.8

Allyl Cyclohexyl Propionate

0.5

BORNAFIX® (IFF)

10.4

CYCLABUTE® (IFF)

9.0

APHERMATE® (IFF)

fifteen

Ethyl methyl phenyl glycidate

1.0

CYCLOGALBANIFF (IFF)

0.5

Isoamyl butyrate

1.0

ISOCYCLOCITRAL® (IFF)

0.5

JASMAL® (IFF)

3.0

Chin

 0.3

Peach Aldehyde

12.0

3-methyl-3 - {[3-methylbut-2-en-1-yloxy] methyl} oxetane

 5.0

Phenyl acetate

4.0

HC VERDOX® (IFF)

28

FRUCTONE® (IFF)

4.0

Claims (10)

1. A method of improving, increasing or modifying a fragrance formulation by adding an acceptable olfactory amount of a compound of formula (I):

in

where  R  be Choose of the  group that  consists  in  C (CH3) C3H7, C (CH3) C4H9, C (CH3) C4H8,

C (CH3) C2H4CHC2H4,

C (CH3) phenyl, C (CH3) CN, C (CH3) COCH3, C (CH3) COC3H7, C (CH3) COC3H6,

10

C (CH3) COCH2CHC2H4.

The method of claim 1 or 2, wherein the fragrance is incorporated into a product selected from perfumes, colognes, eau de colognes, cosmetic products, personal care products, tissue care products, cleaning products and air fresheners 4. The method of claim 3 wherein the cleaning product is selected from the group consisting of detergents, dishwashing compositions, scrubbing compounds and glass cleaners. 5. The method of any one of claims 1 to 4, wherein the amount incorporated into a fragrance is from about 0.005 to about 10 percent by weight. The method of any one of claims 1 to 5, wherein the amount incorporated in a fragrance is from about 0.5 to about 8 percent by weight. 7. The method of any one of claims 1 to 6, wherein the amount incorporated into a fragrance is from about 1 to about 7 percent by weight. 30 8. A method for improving, increasing or modifying a fragrance by adding an acceptable olfactory amount of the compound of the formula below: Wherein R is selected from the group consisting of linear, branched, cyclic or aromatic hydrocarbons that contain single and / or double bonds; carbonyls and carboxy groups. 9. The method of claim 8 wherein the fragrance is incorporated into a product selected from perfumes, colonies, candles, eau de colognes, cosmetic products, personal care products, products for tissue care, cleaning products and air fresheners. 10. The method of claim 9 wherein the cleaning product is selected from the group consisting of soaps, detergents, dishwashing compositions, scrubbing compounds and glass cleaners. The method of claim 9 wherein the product is a personal care product. 12. The method of any of claims 8 to 11, wherein the level is from about 0.005 to about 10 percent by weight. 13. The method of any of claims 8 to 12, wherein the level is from about 0.1 to about 8 percent by weight. 14. The method of any of claims 8 to 12, wherein the level is from about 0.5 to about 5 percent by weight. 10 15.